The outlet stream from combustion processes is a complex mixture of compounds which depends on the specific operating conditions. Thermochemical processes operating under rich fuel conditions enhance the formation of polycyclic aromatic hydrocarbons (PAHs) and soot. PAH play an important role in soot formation, but they can appear adsorbed on soot surface as well as at the gas phase due to their different volatility and molecular weight. Both PAH (the gas phase and adsorbed PAH) fractions are important when considering the total characterization from pyrolytic processes, mainly for determining the emission levels of 16 Environmental Protection Agency (EPA) priority PAH. In this way, an optimized method capable to determine the aromatic compounds in the gas and particle phases in combustion exhaust gases is needed. The method here presented allows the collection and quantification of both the PAH adsorbed on soot and present at the gas phase of the exhaust gases of thermochemical processes. It involves PAH characterization by combining classical Soxhlet extraction of the sample collected, followed by an extract concentration using a rotary evaporator and subsequent micro-concentration under gentle nitrogen stream before the analysis. The EPA-PAH were determined using a gas chromatograph-mass spectrometer (GC-MS). Validation tests using a fully characterized soot, the NIST (National Institute of Standards and Technology) reference material SRM 1650b, and repeatability using diesel surrogate commercial soot named Printex-U, were done. Additionally, experiments of acetylene pyrolysis were carried out and their products analyzed for determining the PAH amount. The results showed good method reliability for the determination of 16 EPA-PAH found in the outlet gases, as well as good recovery for the most of PAH and good prediction for the real samples analyzed. (c) 2013 Elsevier Ltd. All rights reserved.